CN1246383C - Modified block copolymer compsn. - Google Patents

Abstract

The invention discloses a modified block copolymer composition, comprising (1) 100 parts by weight of a modified block copolymer obtained from vinyl aromatic hydrocarbons and conjugated dienes and containing functional groups or a hydrogenated product of the copolymer, The functional group has at least one group selected from hydroxyl, epoxy, amino, silanol, and alkoxysilane groups and (2) 0.5-50 parts by weight selected from silica-based inorganic fillers, metal oxides, and metal hydroxide fillers. The composition has excellent heat resistance, mechanical strength, transparency, abrasion resistance and processability.

Description

Modified block copolymer composition

technical field

The present invention relates to a thermoplastic modified block copolymer composition, comprising a functional group-containing modified block copolymer comprising vinyl arene and conjugated diene, or a hydrogenated product thereof, and at least one selected from silica-based Inorganic fillers, metal oxides, and metal hydroxide fillers.

Background technique

Production of high-performance and high-functional polymer materials by polymer alloy technology combining different kinds of organic high-molecular substances has been researched so far. For example, thermoplastic elastomer compositions that are soft materials having rubber-like properties and that do not require any vulcanization process, and thermoplastic resin compositions that are excellent in molding processability and recyclability have been used in various fields including automotive parts, Household appliance parts, wire jackets, medical instruments, footwear, sundries, and the like. Currently, various materials such as polyolefins, polyurethanes, polyesters, polystyrenes and the like have been developed and commercially available as thermoplastic elastomers and thermoplastic resins.

Among them, vinyl aromatic hydrocarbon-conjugated diene block copolymers such as styrene-butadiene block copolymers and styrene-isoprene block copolymers and the like, and hydrogenated products thereof (sometimes referred to hereinafter as "Hydrogenated block copolymers") have high flexibility and good rubber elasticity at room temperature when they have a low content of styrene. They enable to obtain compositions having excellent molding processability. In addition, if they have a higher content of styrene, they can give transparent thermoplastic resins with outstanding impact resistance, so that they can be used for food packages and containers, home appliance parts, industrial parts, appliances, toys and the like.

However, the functionality and characteristics obtained only by using organic polymer materials are limited, so attempts have been made to overcome the limitations by using combinations of organic polymer materials and inorganic substances as needed.

For example, JP59-131613A discloses an elastomer composition containing hydrogenated block copolymer, hydrocarbon oil, olefin polymer and inorganic filler partially cross-linked with organic peroxides and cross-linking assistants with improved permanent compression set of elastomeric compositions. JP11-256025A discloses a resin composition having excellent electrical conductivity comprising a polyphenylene ether resin hydrogenated block copolymer and an electrically conductive inorganic filler. In addition, JP2001-72853A discloses a thermoplastic resin composition comprising a polycarbonate resin, a styrene-butadiene block copolymer and hollow ceramic particles having excellent moisture absorption resistance and shock absorbing properties.

However, compositions comprising thermoplastic block copolymers and inorganic fillers have not ideally achieved significant improvements in performance because one of the two components is a hydrophobic organic material and the other is a hydrophilic inorganic material, resulting in relatively Low mutual affinity and poor kneading ability.

In order to improve the affinity between thermoplastic block copolymers and different materials, it has been proposed to add functional groups to thermoplastic block copolymers. For example, JP62-54138B and JP62-54140B disclose a Compositions of block copolymers of aromatic hydrocarbons and conjugated dienes with improved affinity for inorganic fillers. In addition, JP4-39495B, JP4-28034B and JP4-38777B disclose a method with improved compatibility with thermoplastic resins, tack-imparting resins and asphalts by adding functional groups to the ends of block copolymers containing vinyl aromatic hydrocarbons and conjugated dienes. affinity composition.

Under these circumstances, for a composition comprising a vinyl aromatic hydrocarbon-conjugated diene block copolymer or its hydrogenated product and an inorganic material, it is necessary to provide a compound having High-performance and highly functional materials.

Disclosure of the invention

The present inventors conducted intensive studies in order to overcome the foregoing problems, and as a result, completed the present invention on the basis of the following findings, that is, a composition having excellent heat resistance, mechanical strength, transparency, abrasion resistance, and processability, which comprises: ( 1) a specific structured modified block copolymer comprising a specific functional group or its hydrogenated product: and (2) at least one filler selected from silica-based inorganic fillers, metal oxides, and metal hydroxides, each of which Components are used in prescribed amounts.

That is, the invention is as follows:

[1] A modified block copolymer composition comprising:

(1) A modified block copolymer consisting of a polymer block A mainly comprising vinyl aromatic hydrocarbon and a polymer block B mainly comprising conjugated diene, or a hydrogenated product thereof, and

(2) at least one filler selected from silica-based inorganic fillers, metal oxides and metal hydroxides,

Wherein the molecular chain of component (1) has functional group at its end, and described functional group has at least one group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilyl group; Component (1) ) has a vinyl aromatic content of 5-95% by weight; the amount of component (2) is 0.5-50 parts by weight based on 100 parts by weight of component (1); and the average particle size of component (2) in the dispersion The size is 0.01-2 μm.

[2] The modified block copolymer composition according to the above [1], further comprising (3) an olefin polymer, wherein the amount of component (3) is 10 to 500 parts by weight based on 100 parts by weight of component (1) .

[3] The modified block copolymer composition according to the above [1] or [2], wherein the block ratio of the vinyl arene in component (1) is not less than 50% of the whole vinyl arene.

[4] The modified block copolymer composition according to [1] or [2] above, wherein component (1) is a hydrogenated product of a modified block copolymer having a hydrogenation rate of not less than 10%, and has ethylene The proportion of structural units of radical bonds to the entire structural units derived from conjugated diene in the hydrogenated product is 10-85%, and the proportion of 1,2C═C units is not higher than 15%.

[5] The modified block copolymer composition according to the above [1] or [2], wherein the molecular chain of component (1) has a functional group at its terminal, selected from the group having the following structural formulas (1)-(14) Group:

-NR ⁹ -R ¹⁰ -OH ----(1)

-N[R ¹⁰ -OH] ₂ ----(2)

-NR ⁹ -R ¹⁰ -Si(OR ¹¹ ) ₃ ----(10)

-N[R ¹⁰ -Si(OR ¹¹ ) ₃ ] ₂ ----(11)

-OR ¹⁰ -Si(OR ¹¹ ) ₃ ----(14)

in

R ⁹ , R ¹² -R ¹⁴ are hydrogen, a hydrocarbon group having 1-24 carbon atoms, or having a group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and having 1-24 carbon atoms The hydrocarbon group of the functional group;

R ¹⁰ is a hydrocarbon chain with 1-30 carbon atoms, or has a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and a hydrocarbon chain with 1-30 carbon atoms;

The hydrocarbon groups R ⁹ , R ¹² -R ¹⁴ and the hydrocarbon chain R ¹⁰ may have elements such as oxygen, nitrogen or silicon bonded in the form of linkages other than hydroxyl, epoxy, silanol, and alkoxysilyl groups ;and

R ¹¹ is hydrogen or an alkyl group having 1-8 carbon atoms.

[6] The modified block copolymer composition according to the above [1] or [2], wherein the molecular chain of component (1) has a functional group at its terminal, selected from the group having the following structural formulas (1)-(9) Group:

-NR ⁹ -R ¹⁰ -OH ----(1)

-N[R ¹⁰ -OH] ₂ ----(2)

in

R ⁹ , R ¹² -R ¹⁴ are hydrogen, a hydrocarbon group having 1-24 carbon atoms, or having a functional group selected from a hydroxide group, an epoxy group, a silanol group, and an alkoxysilyl group and having 1 - a hydrocarbon group of 24 carbon atoms;

R ¹⁰ is a hydrocarbon chain with 1-30 carbon atoms, or has a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and a hydrocarbon chain with 1-30 carbon atoms;

The hydrocarbon groups R ⁹ , R ¹² -R ¹⁴ and the hydrocarbon chain R ¹⁰ may have elements such as oxygen, nitrogen or silicon bonded in the form of linkages other than hydroxyl, epoxy, silanol, and alkoxysilyl groups ;and

R ¹¹ is hydrogen or an alkyl group having 1-8 carbon atoms.

[7] The modified block copolymer composition according to the above [1] or [2], wherein component (2) is at least one selected from silica, wollastonite, montmorillonite, zeolite, alumina, oxide Titanium, magnesium oxide, zinc oxide, slag wool, glass fiber, magnesium hydroxide, aluminum hydroxide, hydrated magnesium silicate, hydrated aluminum silicate, basic magnesium carbonate, and hydrotalcite as fillers.

[8] The modified block copolymer composition according to the above [1] or [2], comprising 0.1 to 20% by weight of the silane coupling agent based on the amount of component (2).

BEST MODE FOR CARRYING OUT THE INVENTION

As described above, the present invention relates to a new composite material having the advantages of organic polymer substances (such as light weight, softness, moldability, etc.) combined with the advantages of inorganic substances (such as heat resistance, high strength, etc.) characteristic material. Especially for a modified block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, or a hydrogenated product thereof, and at least one filler selected from silica-based inorganic fillers, metal oxides and metal hydroxides Compositionally, the present invention provides materials with high performance and high functionality that can effectively exhibit the functionality and characteristics of these two components.

The modified block copolymer used in the present invention is composed of polymer block A mainly containing vinyl aromatic hydrocarbon and polymer block B mainly containing conjugated diene, wherein the molecular chain of the modified block copolymer It has a functional group at its terminal having at least one group selected from hydroxyl, epoxy, amino, silanol and alkoxysilyl groups.

For example, by adding a block copolymer composed of a polymer block A mainly containing vinyl aromatic hydrocarbon and a polymer block B mainly containing conjugated diene with the modifier described below, the modifier Bonding to the living ends of the block copolymer, or its hydrogenated product, can provide a modified block copolymer. The modified block copolymer obtained by this method has a structure, for example represented by one of the following general formulas:

(AB) _n -X,

(BA) _n -X,

A-(BA) _n -X,

B-(AB) _n -X,

X-(AB) _n -X,

XA-(BA) _n -X,

XB-(AB) _n -X,

[(BA)n] _m -X,

[(AB)n] _m -X,

[(BA)nB] _m -X,

[(AB)nA] _m -X

in

A denotes a polymer block mainly comprising vinylarene, and B denotes a polymer block mainly comprising a conjugated diene,

n is an integer of 1 or more, typically 1-5, and m is an integer of 2 or more, typically 2-10.

X is a residue of a modifier having the following functional group.

The polymer block A mainly comprising vinyl arene in the present invention represents a copolymer block comprising vinyl arene and conjugated diene comprising 50% by weight or more, preferably 70% by weight or more of vinyl arene. segments, and/or homopolymer blocks of vinyl aromatic hydrocarbons. Polymer block B mainly comprising a conjugated diene means a copolymer block comprising a conjugated diene and a vinyl arene comprising more than 50% by weight, preferably 60% by weight or more of a conjugated diene, and/ or homopolymer blocks of conjugated dienes. The vinylarene units can be distributed uniformly or in a tapered (tapered pattern) in the copolymer block. The copolymer block may have multiple domains in which the vinylarene units are uniformly distributed and/or multiple domains in which the units are distributed in a tapered shape.

The modified block copolymer used in the present invention may be an optional mixture of modified block copolymers represented by the aforementioned general formula.

As a method for producing a block copolymer before modification (hereinafter sometimes simply referred to as "block copolymer"), for example, there can be mentioned those disclosed in, e.g., JP43-17979B, JP49-36957B, JP48-4106B , and those of JP59-166518A.

Vinyl aromatics useful in the present invention include, for example, styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α- Methylstyrene, vinylnaphthalene, vinylanthracene and the like are used singly or in combination of two or more, among which styrene is generally used. Conjugated dienes useful in the present invention include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1, 3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, alone or in combination of two or more, of which 1,3-butadiene and isoprene are generally used alkene.

Solvents useful in producing the block copolymers of the present invention include, for example, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane alkanes, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatics such as benzene, toluene, ethylbenzene, and xylene. These solvents may be used alone or in combination of two or more.

Polymerization initiators used to produce block copolymers include organolithium compounds. Organolithium compounds are those having one or more lithium atoms in the molecule. For example, there are ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, Prenyl dilithium, and the like. These initiators may be used alone or in combination of two or more. The organolithium compound can be added in batches during the production (polymerization) of the block copolymer.

In the present invention, polar compounds and randomizers can be used to control the rate of polymerization, the micro-structure of the polymerized conjugated diene moiety, and the degree of concentration of the conjugated diene and vinyl aromatic hydrocarbon in the production of block copolymers. Emergence of random copolymerization. Polar compounds and randomizers include ethers, amines, thioethers, phosphines, phosphoramides, potassium or sodium salts of alkylbenzene sulfonates, potassium or sodium alkoxylates and the like. Examples of practical ethers include dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. Amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines. Phosphine and phosphoramidites include triphenylphosphine, hexamethylphosphoramide, and the like.

The polymerization reaction temperature when producing the block copolymer according to the present invention is preferably -10 to 150°C, more preferably 30-120°C. Although depending on the reaction conditions, the polymerization reaction time is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization reaction system should preferably be under an atmosphere of an inert gas such as nitrogen. The polymerization pressure is not critical provided that the pressure is sufficient to maintain the monomer and solvent in the liquid phase within the aforementioned polymerization temperature range. In addition, it is preferable to take care that impurities which deactivate the catalyst and the active polymer, such as water, oxygen, carbon dioxide gas and the like, are prevented from entering the polymerization reaction system.

The component (1) used in the present invention, that is, the modified block copolymer and its hydrogenated product is a modified block copolymer having a functional group having at least one bonded to A group selected from hydroxyl group, epoxy group, amino group, silanol group and alkoxysilyl group at the end of its molecular chain. As a method for producing those modified block copolymers having these functional groups as described above, there can be mentioned a method in which a block copolymer is mixed with a modifying agent having the aforementioned functional groups or Known technology protects the method of reacting modifiers of the aforementioned functional groups. Although hydroxyl groups and amino groups may be in the form of organometallic salts according to their kind after the modifier reaction, in this case, they can be converted into hydroxyl groups and amino groups by treating with active hydrogen-containing compounds such as water and alcohol.

In the present invention, after the block copolymer undergoes a reaction with a modifying agent on its living end, a part of the unmodified block copolymer may remain in the mixture. The unmodified block copolymer may be present in the mixture with the modified block copolymer in a proportion of preferably not higher than 60% by weight, more preferably not higher than 50% by weight.

Examples having at least one functional group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilyl group include those selected from functional groups represented by the following general formulas (1)-(14):

-NR ⁹ -R ¹⁰ -OH ----(1)

-N[R ¹⁰ -OH] ₂ ----(2)

-NR ⁹ -R ¹⁰ -Si(OR ¹¹ ) ₃ ----(10)

-N[R ¹⁰ -Si(OR ¹¹ ) ₃ ] ₂ ----(11)

-OR ¹⁰ -Si(OR ¹¹ ) ₃ ----(14)

in

R ⁹ , R ¹² -R ¹⁴ are hydrogen, a hydrocarbon group having 1-24 carbon atoms, or having a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and having 1-24 A hydrocarbon group of carbon atoms;

R ¹⁰ is a hydrocarbon chain with 1-30 carbon atoms, or has a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and a hydrocarbon chain with 1-30 carbon atoms;

The hydrocarbon groups R ⁹ , R ¹² -R ¹⁴ and the hydrocarbon chain R ¹⁰ may have elements such as oxygen, nitrogen or silicon bonded in the form of linkages other than hydroxyl, epoxy, silanol, and alkoxysilyl groups ;and

R ¹¹ is hydrogen or an alkyl group having 1-8 carbon atoms.

Modifiers useful in producing the modified block copolymers of the present invention include, for example, tetraglycidyl m-xylylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, tetraglycidyl yl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl-o-toluidine, gamma-glycidyloxyethyl-trimethoxysilane, gamma - Glycidoxypropyltrimethoxysilane, γ-Glycidoxybutyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltripropoxy γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyl triphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-shrink Glyceryloxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidyloxy propylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyl Dimethylmethoxysilane, γ-glycidoxypropyl diethylethoxysilane, γ-glycidoxypropyl dimethylethoxysilane, γ-glycidoxypropyl diethylethoxysilane Methylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, bis(γ-glycidoxypropyl ) dimethoxysilane, bis(γ-glycidoxypropyl)diethoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl) base) dibutoxysilane, bis(γ-glycidyloxypropyl) diphenoxysilane, bis(γ-glycidyloxypropyl)methylmethoxysilane, bis(γ-glycidyloxypropyl) propyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ -glycidyloxypropyl)methylphenoxysilane, tris(γ-glycidoxypropyl)methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methyl Acryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis(γ-methacrylic Acyloxypropyl)dimethoxysilane, Tris(γ-methacryloxypropyl)methoxysilane, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-cyclo Oxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane, β-(3,4-epoxycyclohexyl)propyl-trimethyl Oxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β-(3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β-(3,4-cyclo Oxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,-4-epoxycyclohexyl)ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl ) ethyl-diethylethoxysilane, β-(3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl) ethyl- Dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbenzene Oxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropenyloxy- Silane, 1,3-dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolinone, N,N'-dimethylpropylene urea, and N-methylpyrrolidone.

The reaction with the aforementioned modifiers can result in polymer embeddings comprising functional groups having bonded thereto modifier residues, i.e., functional groups selected from hydroxyl, epoxy, amino, silanol, and alkoxysilyl groups. Modified block copolymers of segment A and/or polymer block B, or hydrogenated products of modified block copolymers. The location of the modified block copolymer to which the modifier residue is bonded is not critical, but it is preferred that it is bonded to polymer block A to obtain a combination with excellent physical properties at high temperatures thing.

The amount of the modifier comprising a functional group for addition reaction with the active end of the block copolymer in the present invention should preferably be higher than 0.5 equivalents, more preferably higher than 0.7 equivalents, and most preferably higher than 0.9 equivalents, based on one equivalent The block copolymer living end, but it should preferably not be higher than 10 equivalents, more preferably not higher than 5 equivalents, and most preferably not higher than 4 equivalents, based on one equivalent of block copolymer living ends.

The amount of the active end of the block copolymer in the present invention can be calculated from the amount of the organolithium compound used in the polymerization reaction and the number of lithium atoms bonded to the organolithium compound.

The hydrogenated product of the modified block copolymer of the present invention can be obtained by hydrogenating the modified block copolymer produced by the aforementioned process. The hydrogenation catalyst used for the hydrogenation is not critical and may be, for example, conventionally known catalysts (i) heterogeneous supported catalysts such as Ni, Pt, Pd, and Ru on supported carbon, silica, alumina diatomaceous earth or the like metal, (ii) so-called Ziegler hydrogenation catalysts employing transition metal salts such as organic acid salts or Ni, Co, Fe, or Cr and reducing agents such as organoaluminum acetylacetones, (iii) homogeneous hydrogenation catalysts such as so-called organic Metal complexes such as organometallic compounds of Ti, Ru, Rh, Zr, or the like.

Actually, hydrogenation catalysts such as those disclosed in JP42-8704B, JP43-6636B, JP63-4841B, JP1-37970B, JP1-53851B, and JP2-9041B can be used. Preferred hydrogenation catalysts include mixtures of titanocene compounds and reducing organometallic compounds.

Titanocene compounds disclosed in, for example, JP8-109219A can be used, but actually there can be mentioned ligands containing at least one kind of cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton having a substituted or unsubstituted cyclopentadienyl skeleton, such as di Cyclopentadienyl titanium dichloride, or a compound of monopentamethylcyclopentadienyl titanium trichloride. Reducing organometallic compounds include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, or organozinc compounds.

The hydrogenation reaction is generally carried out at a temperature in the range of 0-200°C, preferably 30-150°C. The hydrogen pressure for the hydrogenation reaction is 0.1-15 MPa, preferably 0.2-10 MPa, more preferably 0.3-5 MPa. The hydrogenation reaction time is 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be carried out in a batch process, a continuous process, or a combination thereof.

The structural unit derived from the conjugated diene in the hydrogenated product of the modified block copolymer can be expressed as the following general formulas (a)-(e):

wherein R ¹ -R ⁸ independently represent hydrogen, halogen, aliphatic hydrocarbons with 1-20 carbon atoms, or aromatic hydrocarbons with 1-20 carbon atoms, and they may be the same or different from each other;

Structural formula (a) represents a cis structure, and

Structural formula (b) represents a trans structure.

In order to obtain a composition with good thermal stability, the hydrogenation rate of the hydrogenated modified block copolymer should preferably not be lower than 10%, more preferably 30-100%, most preferably 50-100%. The hydrogenation rate of the hydrogenated modified block copolymer can be expressed as the following equation on the basis of the above structural formulas (a)-(e).

Hydrogenation rate=(c+e)/(a+b+c+d+e)×100

In addition, considering the productivity of the block copolymer and the softness and impact resistance of the resulting composition, the ratio of the structural unit having a vinyl bond to the entire structural unit derived from a conjugated diene is important in hydrogenation-modified block copolymers. The proportion in should preferably be 10-85%, more preferably 30-75%, most preferably 35-70%. The ratio of the ratio of the structural unit having a vinyl bond to the entire structural unit derived from the conjugated diene can be expressed as the following equation on the basis of the above structural formulas (a)-(e).

Proportion of vinyl bonds = (d+e)/(a+b+c+d+e)×100

In addition, in the hydrogenation-modified block copolymer, the ratio of 1,2C=C units to the entire structural units derived from conjugated diene should preferably be no higher than 15%, more preferably 0-7%, most preferably 0 -3%, which gives a composition with good thermal stability. The proportion of 1,2C=C units based on the total structural units derived from the conjugated diene can be expressed as the following equation on the basis of the above structural formulas (a)-(e):

1, 2C=C unit ratio=d/(a+b+c+d+e)×100

The content of vinyl arene in the above-mentioned modified block copolymer or its hydrogenated product can be determined by using an ultraviolet spectrophotometer and the like. The ratio of the structural unit having a vinyl bond to the entire structural unit derived from the conjugated diene in the hydrogenation-modified block copolymer and the hydrogenation rate of the hydrogenation-modified block copolymer can be determined by using nuclear magnetic resonance (NMR) determined by the system. In addition, the content of vinyl arene in the hydrogenated modified block copolymer can be understood as the content of vinyl arene in the copolymer before hydrogenation.

The final modified block copolymer or its hydrogenated product can be obtained by removing the catalyst residue from the modified block copolymer or its hydrogenated product produced by the aforementioned process, if necessary, and separating the solvent. As a method for separating the solvent, there can be mentioned, for example, a method comprising adding a polar solvent such as acetone or alcohol, which is a poor solvent for the polymer, to the polymer solution to precipitate the polymer and then recovering the polymer; comprising dissolving the polymer solution in A method that involves pouring into hot water with stirring and stripping with steam to remove the solvent and recover the polymer; or a method that involves direct heating of the polymer solution to evaporate and remove the solvent.

Stabilizers that may be added to the modified block copolymer or its hydrogenated product used in the present invention include various phenolic stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers.

The content of vinyl aromatic hydrocarbon in component (1) used in the present invention should be 5-95% by weight, preferably 8-80% by weight, more preferably 10-70% by weight. If it is lower than 5% by weight, the resulting composition undesirably has poor permanent compression set and tensile strength, and if it is higher than 95% by weight, the resulting composition undesirably has lower impact resistance. If the content of vinyl aromatic hydrocarbon is generally not higher than 60% by weight, specifically not higher than 55% by weight, component (1) has properties as a thermoplastic elastomer, and if it is generally higher than 60% by weight, specifically 65% By weight or more, component (1) has properties as a thermoplastic resin.

Component (1) should preferably have a weight average molecular weight of 30,000 or more (in consideration of the tensile strength of the composition), 1,000,000 or less (in consideration of processability), more preferably 60,000-800,000, still more preferably 70,000-600,000. The weight-average molecular weight can be determined from the peak molecular weight shown in the chromatogram obtained by using gel permeation chromatography (GPC) on a calibration curve measured from commercially available standard polystyrene (drawn by using the peak molecular weight of standard polystyrene). out) based on the obtained.

The block ratio of the vinyl arene of component (1) should not be lower than 50%, preferably 50-97% by weight, further more preferably 60-95% by weight, based on the whole vinyl arene in component (1), such Compositions with excellent permanent compression set were obtained. The block ratio of vinyl arene here refers to the proportion of vinyl arene polymer blocks present in component (1).

The block ratio of vinylarene can be determined according to the following equation by using the vinylarene polymer block components by oxidative decomposition of the block copolymer with tert-butyl hydroperoxide over an osmium tetrachloride catalyst (is A process such as that disclosed in I. M. KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) except that vinyl aromatic polymer block components having a degree of polymerization of about 30 or less are excluded.

The block rate of vinyl arene (%)=[(the mass of vinyl arene polymer block in the block copolymer)/(the mass of the whole vinyl arene in the block copolymer)]×100

The filler used as component (2) in the present invention is described below. Component (2) is at least one filler selected from silica-based inorganic fillers, metal oxides, and metal hydroxides.

Silica-based inorganic fillers here mean solid particles mainly comprising SiO ₂ or Si ₃ Al as structural units. For example, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, and inorganic fibrous materials such as glass fibers can be used. In addition, silica-based inorganic fillers having hydrophobic surfaces, combinations of two or more kinds of silica-based inorganic fillers, and mixtures of silica-based inorganic fillers and non-silica-based inorganic fillers may be used. Usable silica includes, for example, so-called anhydrous white carbon, hydrous white carbon, synthetic silicate white carbon, and colloidal silica.

Metal oxides refer to solid particles mainly composed of structural units represented by the chemical formula M _x O _y , where M is a metal atom and x and y are integers 1-6, respectively, such as alumina, titanium oxide, magnesium oxide, and oxide zinc. Combinations of two or more metal oxides and mixtures of metal oxides and inorganic fillers other than metal oxides may be used. Metal hydroxides that can be used refer to hydrated inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, hydroxide Barium, hydrated tin oxide, hydrates of inorganic metal compounds such as borax. Combinations of two or more metal hydroxides and mixtures of metal hydroxides and inorganic fillers other than metal hydroxides may be used.

The fillers used in the present invention should preferably be silica and glass fibers, with silica being especially preferred.

In the present invention, the average particle size of the filler in the dispersion is preferably 0.01-2 μm, more preferably 0.03-1 μm, most preferably 0.05-0.5 μm, considering that the filler is dispersed in the composition and fully plays the role of the added filler. The average particle size of the filler in the dispersion can be determined by observing the dispersed state of the filler with a transmission electron microscope (TEM) and using an image analyzer.

The amount of component (2) should be 0.5-50 parts by weight, preferably 3-40 parts by weight, based on 100 parts by weight of component (1). If the added amount of component (2) is less than 0.5 parts by weight, the filler exhibits an addition effect, while if it is more than 50 parts by weight, component (2) is not well dispersed and processability and mechanical strength become undesirably lowered .

In addition to the aforementioned components (1) and (2), the composition of the present invention may further contain an olefin polymer (hereinafter sometimes referred to as component (3)). As the olefin polymer, there may be mentioned those mainly containing α-olefins such as ethylene, propylene and the like, for example, polyethylene, polypropylene, ethylene-propylene copolymer, chlorinated polyethylene and the like. The olefin polymer used may include, for example, a small amount of vinyl monomers in addition to olefins such as ethylene, propylene and the like. For example, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid derivative copolymers and the like can be mentioned. In addition, olefin polymers may also include hydrogenated products of polymers comprising conjugated diene monomers such as butadiene, isoprene and the like. These resins may be used in admixture of two or more thereof. Polypropylene, or mixtures of polypropylene and ethylene-propylene copolymers, are preferred in terms of processability and mechanical properties of the resulting composition.

Considering the permanent compression set of the composition, the balance between tensile strength and elasticity, the amount of component (3) should be based on 100 parts by weight of component (1), preferably 10-500 parts by weight, more preferably 20-300 parts by weight parts by weight.

In the modified block copolymer composition of the present invention, component (1), that is, the modified block copolymer or its hydrogenated product contains specific functional groups so that they have a high affinity with component (2), the filler properties, allowing the filler to be finely dispersed in the copolymer while effectively exhibiting interactions between them due to chemical bonds such as hydrogen bonds. Therefore, the object of the present invention, that is, a modified block copolymer composition excellent in heat resistance, mechanical strength, transparency, abrasion resistance, and processability, can be obtained. In addition, a modified block copolymer composition excellent in permanent compression set, impact resistance and processability can also be obtained.

The modified block copolymer composition of the present invention may further include an introduced silane coupling agent. Silane coupling agents are used to make the interaction between components (1) and (2) closer and contain a group. The silane coupling agent used may include those generally used for inorganic fillers such as silica, for example, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxy Propyltriethoxysilane, p-Styryltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N- 2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene ) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

Particularly preferred silane coupling agents of the present invention are, for example, those having polysulfide linkages linking together two or more mercapto and/or sulfur atoms with silanol groups or alkoxysilane groups. These silane coupling agents include, for example, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis-[3-(triethoxysilyl)-propyl]-tetra Sulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[3-(triethoxysilyl)-propyl]-trisulfide, di -[2-(triethoxysilyl)-ethyl]-tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl-N,N-dimethyl-thiocarbamoyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, and 3-trimethyl Oxysilylpropylbenzothiazole tetrasulfide.

The amount of the silane coupling agent added should be preferably 0.1-20% by weight based on the amount of component (2), more preferably 0.5-18% by weight, even more preferably 1-15% by weight, so as to fully exhibit the reinforcing effect of the filler.

Silane coupling agents can be used in combination with sulfur and organic peroxides.

The modified block copolymer composition of the present invention can further use a block copolymer different from the modified block copolymer used in the present invention or its hydrogenated product, or its hydrogenated product, such as non-modified block copolymer, thermoplastic resin , rubbery polymers and the like.

Thermoplastic resins include block copolymer resins of vinyl aromatic compounds and conjugated dienes other than modified block copolymers or their hydrogenated products as defined in this invention; vinyl aromatic compound resins such as polystyrene; vinyl Aromatics with other vinyl monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylates such as methyl acrylate, methacrylic acid and methacrylates such as methacrylic acid Methyl ester, acrylonitrile, or methacrylonitrile copolymer resins; rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene-copolymer resins (ABS); methyl acrylate-butanediene ethylene-styrene-copolymer resins (MBS); poly(vinyl acetate) resins, i.e., copolymers comprising vinyl acetate with other monomers polymerizable therewith and having a vinyl acetate content of 50% by weight or more, and the hydrolyzate of the resin; polymers of acrylic acid and its esters and/or amido groups; polymers of methacrylic acid and its esters and/or amido groups; polyacrylate resins, i.e., 50% by weight or more of the aforementioned acrylic acid Copolymers of monomers and other copolymerizable monomers; polymers of acrylonitrile and/or methacrylonitrile; nitrile resins, that is, copolymers of 50% by weight or more of the aforementioned acrylonitrile monomers and other copolymerizable monomers; Aliphatic polyamide resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, or nylon-6-nylon-12 copolymers; aromatic polyamide resins such as polyphenylene isophthalamide, polyphenylene terephthalamide, or polym-xylene diamine; polyester resins such as dibasic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic , P, P'-dicarboxydiphenyl, 2,6-naphthalene dicarboxylic acid, or its derivatives with diol (or diol) components such as ethylene glycol, propylene glycol, 1,4-butanediol , 1,6-hexanediol, 1,4-cyclohexanediol, P-xylylene glycol, or condensation polymers of bisphenol A; polyester diols such as poly(adipate 1,4- butylene ester), poly(1,6-hexanediate), or polycaprolactone; polyether diols such as polyethylene glycol, polypropylene glycol, or polyoxytetramethylene glycol; by A diol component selected from diols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol and a diisocyanate component such as tolylene diisocyanate, 4,4'-diphenyl Thermoplastic polyurethane polymers produced by polyaddition of methyl methane diisocyanate, or hexamethylene diisocyanate; polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'- Propane carbonate; polysulfone resins such as poly(ether sulfone), poly(4,4'-bisphenol ether sulfone), and poly(sulfide sulfone); polymers of formaldehyde or trioxane; polyoxymethylene Copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, epoxides, isocyanates, or vinyl compounds; polyphenylene ether resins such as poly(2,6-dimethyl-1,4- phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide, or poly 4,4'-diphenylene sulfide; polyimide, polyaminobismaleimide (poly bismaleimide), bismaleimide-triazine resins; polyimide resins such as polyamidoimide, and polyetherimide.

The number average molecular weight of those thermoplastic resins should preferably be not less than 1,000, more preferably 5,000-5,000,000, still more preferably 10,000-1,000,000.

Combinations of two or more of those thermoplastic resins may be used as necessary.

Rubbery polymers include butadiene rubber and its hydrogenated products, styrene-butadiene rubber and its hydrogenated products, isoprene rubbers other than modified block copolymers and their hydrogenated products as defined in the present invention, Acrylonitrile-butadiene rubber and its hydrogenated products, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, butyl rubber, ethylene-butene rubber, Ethylene-hexene rubber, ethylene-octene rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylate-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and its hydrogenated products, styrene-isoprene block copolymer, and natural rubber. Those rubbery polymers may be modified rubbers with attached functional groups.

Among the thermoplastic resins and rubbery polymers as described above, most preferably, polystyrene resins and polyphenylene ether resins may be mentioned.

In addition, optional additives may be incorporated according to various end uses as long as they do not adversely affect the present invention. The type of additive is not critical, provided they are generally used in formulating thermoplastic resins and rubbery polymers.

For example, rubber softeners such as naphthenic acid and/or alkanoic acid, or polybutene, low molecular weight polybutadiene, paraffin, organopolysiloxane, and mineral oil may be mentioned; inorganic fillers such as calcium carbonate, carbonic acid Magnesium, calcium sulfate, and barium sulfate; pigments such as carbon black and iron oxide; lubricants such as stearic acid, ulnic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene di-stearate Amides; release agents; plasticizers; antioxidants such as hindered phenol antioxidants, and phosphorus-containing heat stabilizers; hindered amine light stabilizers; benzotriazole UV absorbers; flame retardants; static inhibitors; enhance Agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; colorants; other additives and combinations thereof; and those described, for example, in "Agents for Rubber-Plastic Compounding" (Edited by Rubber Digest-Sha Co., Ltd.).

The method used to produce the modified block copolymer composition of the present invention is not specific, and any known process may be used.

For example, production can be performed by using a melt kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, heating roll, Brabender, and various kneaders. In production, the components can be introduced in any order, for example, all the components can be kneaded at once, or optional components can be kneaded and the remaining components can be sequentially or batched under kneading join in

In one embodiment, the production can be carried out by dispersing component (2) in a solution obtained after the hydrogenation reaction is carried out after the polymerization of component (1), or by dispersing component (1) in a solvent In the resulting solution, all were mixed, and the mixture was then heated to remove the solvent.

In the present invention, a melt kneading process using an extruder is preferable in terms of productivity, but in order to produce a highly dispersible composition, mixing in a solvent is specifically recommended.

The modified block copolymer composition of the present invention can be connected with the filler through the specific functional group (as described above) contained in the modified block copolymer or its hydrogenated product (due to chemical bonding such as hydrogen bonding between the two knot) and behave as a composite state. The appearance of this complex state can be confirmed by the fact that if components (1) and (2) are mixed in solution, or if component (2) is added to a solution of component (1) and then mixed, even if left for a while Over time, a small amount of component (2) separates and settles from the mixed solution, while most floats in a finely dispersed state. Especially when component (2) has a small average particle size (eg secondary particle size below 50 μm), the presence of component (2) settling to the bottom of the container is substantially invisible. On the other hand, if component (1) does not have any of the functional groups defined in the present invention, almost all of component (2) consists of the mixture of component (1) and component (2) after standing for a period of time The solution settled down to the bottom of the container.

The block copolymer composition of the present invention can be molded by conventional thermoplastic resin molding machines. It can be used as various molded products such as sheets, films, various forms of injection molded products, blow molded products, pressure molded products, vacuum molded products, extrusion molded products and the like. Those molded articles can be used for food packaging materials, medical instrument materials, home appliances and parts thereof, materials for automobile parts, industrial products, daily necessities, toys and the like, and materials for footwear and the like.

Embodiment 1-17 and comparative example 1-15

The present invention is specifically described based on the following examples, but the present invention is not intended to be limited to those

Example.

In the following examples, the physical properties of the modified block copolymer or its hydrogenated product and the modified block copolymer composition were determined according to the procedure described below. In the Examples, the modified block copolymer and the modified block copolymer composition are simply referred to as "block copolymer" and "block copolymer composition", respectively.

1. Characterization of block copolymers and their hydrogenated products

(1) Styrene content

The styrene content was calculated from the absorbance intensity at 262 nm using a UV spectrophotometer (HITACHI UV 200).

(2) Hydrogenation rate of polybutadiene moiety, ratio of vinyl bonds, and ratio of 1,2C=C units These were measured using a nuclear magnetic resonance apparatus (DPX-400, available from BRUCKER Corporation).

(3) Weight average molecular weight

GPC (device: LC10 manufactured by SHIMADZU Corporation, column: Shimpac GPC805+GPC804+GPC804+GPC803 manufactured by SHIMADZU Corporation) was used for measurement. Tetrahydrofuran was used as a solvent, and the measurement temperature was 35°C. From the peak molecular weight on the chromatogram, the weight-average molecular weight is determined from a calibration curve which has been obtained from the measurement of commercially available standard polystyrene by using the peak molecular weight of the standard polystyrene.

(4) Proportion of unmodified block copolymer

The GPC column filled with silica-based gel has the property of adsorbing the modified component, and the measurement is performed using this property. For the sample solution comprising the modified block copolymer and the internal standard polystyrene with low molecular weight, the ratio of the modified block copolymer to the standard polystyrene on the chromatogram obtained in (3) above was compared with that in The ratio of the modified block copolymer on the chromatogram obtained by GPC using a silica column (Zorbax: a column manufactured by DuPont Company) was compared with that of standard polystyrene, and it was determined from the difference between the two ratios that it was absorbed into Amount of component on silica column. The proportion of unmodified block copolymer is the proportion of copolymer that is not absorbed onto the silica pillars.

(5) Content of styrene homopolymer block (block ratio)

The styrene homopolymer blocks obtained by the oxidative decomposition of the copolymer according to the above process were analyzed with an ultraviolet radiation spectrophotometer and the block ratio was determined by using the following formula.

Block ratio (%)=[(% weight of styrene homopolymer block in block copolymer before hydrogenation)/(wt% weight of whole styrene in block copolymer before hydrogenation)]×100

2. Measurement of Physical Properties of Block Copolymer Compositions

(1) Transparency (haze)

The block copolymer composition was molded under compression into a sheet having a thickness of 2 mm as a test specimen, and then measured according to ASTM-D1003.

(2) Heat resistance

The dynamic storage modulus (E') of the block copolymer composition was measured as a function of temperature using a DMA spectrometer (983DMA, obtained from DuPont Company) under the following conditions to evaluate the resistance in the high temperature region at the inflection point temperature. hot sex.

The thickness of the test sample: 2mm.

Length of span: 16mm.

Measuring temperature: 0°C-200°C.

Temperature increase rate: 2°C/min.

Measurement Frequency Mode: Resonant Frequency.

(3) Abrasion resistance

The weight change of the test specimen was measured before and after being rubbed 1000 times with a color fastness rubbing tester (AB-301, available from TESTERSANGYO Co., Ltd.).

(4) Processing performance

The block copolymer composition was melt-kneaded at 200° C. with a twin-screw open roll, and processability was evaluated according to the state of being wound on a roll according to the following three grades:

○: Good state wound on a roll

Δ: Could not be wound on a roll, but could be formed into a sheet.

×: Cannot be formed into a sheet, and kneading is basically difficult.

(5) JIS-A hardness

The measurement is performed in accordance with JIS-K6301.

(6) Permanent compression deformation (%)

The measurement was performed in accordance with JIS-K-6301 (70° C.×22 hours).

(7) Tensile strength (MPa) and tensile elongation (%)

The measurement is performed in accordance with JIS-K-6251. The elongation speed was 500 mm/min.

(8) Bending strength (MPa)

Measurements are made according to ASTM-D790.

(9) Notched Izod Impact Strength (J/m)

The measurement is performed in accordance with JIS-K-7110.

(10) The average particle size of the filler in the dispersion (μm)

The average particle size of the filler in the dispersion was determined using transmission electron microscopy (TEM). The TEM measurement enables the dispersion state of the filler to be observed at a magnification of 5000-100,000 and the number average particle size in the dispersion is determined using an image analysis system (Win ROOF, an image analysis system manufactured by MITANI Corporation). The number average particle size (dn) in a dispersion is defined as follows:

dn=∑nidi/∑ni (ni is the number of particles with particle size di)

As used herein, the term "particle size" refers to the diameter of an equivalent ring having the same area as the particle.

3. Preparation of hydrogenation catalyst

In the preparation of block copolymers as described below, the hydrogenation catalyst used in the hydrogenation reaction was prepared according to the following method:

(1) Hydrogenation Catalyst I

1 liter of anhydrous purified cyclohexane was charged into a reaction vessel flushed with nitrogen, 100 mmol of bis(η5-cyclopentadienyl) titanium dichloride was added thereto and a solution containing 200 mmol of trimethylaluminum was added under sufficient stirring. n-hexane solution. The reaction proceeds at room temperature for about three days.

(2) Hydrogenation Catalyst II

2 liters of anhydrous purified cyclohexane was charged into a reaction vessel flushed with nitrogen, and 40 mmol of bis(η5-cyclopentadienyl)titanium bis-(p-tolyl) and 150 g of 1,000 molecular weight were added thereto. , 2-polybutadiene (proportion of vinyl bonds: about 85%) and then a cyclohexane solution containing 60 mmol n-butyllithium was added. Immediately after the reaction proceeded at room temperature for 5 minutes, 40 mmol n-butanol was added with stirring and the contents were kept at room temperature.

4. Introduced components

In the following examples, the following compounds were used as components:

(1) Block copolymer

Block copolymers were prepared by the procedure described below. The properties of the resulting block copolymers are given in Tables 1 and 2.

(2) Filler silica A:

Precipitated silica (Sipernat 500LS: secondary particle size 3.5 μm; obtained from Degussa Huls AG)

Silica B: highly dispersible hydrous silica (HDK N20 from Wacker Asahikasei Silicone Co., Ltd.)

Silica C: wet silica (Ultrasil VN3: secondary particle size 16 μm; obtained from Degussa)

(3) Olefin polymer

Polypropylene (PM801A from Montel SDK Ltd.)

(4) Silane coupling agent

Bis-(3-triethoxysilylpropyl)-tetrasulfide (from Degussa, hereinafter referred to as "Si69")

(5) Other components

Rubber softener: Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.

Polystyrene resin: Polystyrene 685, manufactured by A & M Styrenic Co., Ltd.

Polyphenylene ether resin: poly(2,6-dimethyl-1,4-phenylene ether) (reduced viscosity, 0.54).

5. Preparation of Block Copolymers

1) Polymer 1

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 10 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 80 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 10 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, tetraglycidyl-1,3-diaminomethylcyclohexane was reacted as a modifier (hereinafter referred to as modifier M1) in an equivalent molar amount to n-butyllithium used for the polymerization reaction. The resulting modified block copolymer had a styrene content of 20% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 50%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The obtained hydrogenated modified block copolymer (polymer 1) has properties as shown in Table 1. In this case, the proportion of the unmodified block copolymer included in Polymer 1 was 20% by weight.

2) Polymer 2

Polymer 2 was prepared following the same procedure as Polymer 1 except that the modifier was omitted. The properties of Polymer 2 are given in Table 1.

3) Polymer 3

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 10 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 60 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 10 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, a solution containing 20 parts by weight of butadiene in cyclohexane was further added and then polymerization was performed at 70°C for 1 hour. Then, tetraglycidyl m-xylylenediamine was reacted as a modifier (hereinafter referred to as modifier M2) in an equivalent molar amount relative to n-butyllithium used in the polymerization reaction. The resulting modified block copolymer had a styrene content of 20% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 50%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The obtained hydrogenated modified block copolymer (polymer 3) has properties as shown in Table 1. In this case, the proportion of the unmodified block copolymer included in Polymer 3 was 20% by weight.

4) Polymer 4

Polymer 4 was prepared following the same procedure as Polymer 3 except that the modifier was omitted. The properties of Polymer 4 are given in Table 1.

5) Polymer 5

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 20 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 60 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 20 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, the modifier M1 was reacted in a 1/4 equivalent molar amount of n-butyllithium used for the polymerization reaction. The resulting modified block copolymer had a styrene content of 40% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 17%.

Add to the modified block copolymer obtained above for deactivation, then add 2-t-butyl-6-(3-t-butyl group based on 100 parts by weight of modified block copolymer in an amount of 0.3 -2-Hydroxy-5-methylbenzyl)-4-methylphenylacrylate as a stabilizer. A solution of the modified block copolymer in cyclohexane was subjected to steam stripping to remove cyclohexane therefrom, which produced a modified block copolymer (polymer 5) having the properties shown in Table 1 . In this case, the proportion of the unmodified block copolymer included in Polymer 5 was 30% by weight.

6) Polymer 6

Polymer 6 was prepared following the same procedure as polymer 5, except that instead of modifier M1, _SiCl4 was used in 1/4 equivalent molar amount relative to n-butyllithium used for polymerization. The properties of Polymer 6 are given in Table 1.

7) Polymer 7

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 35 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. Subsequently, n-butyllithium and tetramethylethylenediamine were added and after polymerization at 70° C. for 1 hour, a mixture containing 20 parts by weight of previously refined butadiene and 10 parts by weight of styrene (20% concentration) in cyclohexane was added. weight) and then polymerized at 70°C for 1 hour. In addition, a solution containing 35 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propaneamine is used as a modifier (hereinafter referred to as modifier M3) to be relatively used in polymerization The equivalent molar amount of n-butyllithium reacted. The resulting modified block copolymer had a styrene content of 80% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 35%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The obtained hydrogenated modified block copolymer (polymer 7) has properties as shown in Table 1. In this case, the proportion of the unmodified block copolymer included in Polymer 7 was 40% by weight.

8) Polymer 8

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 15 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 70 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 15 parts by weight of styrene in cyclohexane was added and then polymerization was performed at 70° C. for 1 hour. Then, γ-glycidoxypropyltriethoxysilane was reacted as a modifier (hereinafter referred to as "modifier M4") in an equivalent molar amount to n-butyllithium used for the polymerization reaction. The resulting modified block copolymer had a styrene content of 30% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 40%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The solution of the hydrogenated modified block copolymer in cyclohexane was subjected to steam stripping to remove cyclohexane therefrom, which produced a hydrogenated modified block copolymer (polymer 8) having the properties shown in Table 1 . In this case, the proportion of the unmodified block copolymer included in Polymer 8 was 25% by weight.

9) Polymer 9

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 8 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After subsequent addition of n-butyllithium and tetramethylethylenediamine and polymerization at 70° C. for 1 hour, 85 parts by weight of previously refined isoprene (concentration 20% by weight) in cyclohexane was added and subsequently Polymerization was carried out at 70°C for 1 hour. In addition, a solution containing 7 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, the modifier M1 was reacted in a 1/4 equivalent molar amount of n-butyllithium used for the polymerization reaction. The resulting modified block copolymer had a styrene content of 15% by weight, wherein the proportion of vinyl bonds in the polyisoprene fraction was 30%.

Add to the modified block copolymer obtained above for deactivation, then add 2-t-butyl-6-(3-t-butyl group based on 100 parts by weight of modified block copolymer in an amount of 0.3 -2-Hydroxy-5-methylbenzyl)-4-methylphenylacrylate as a stabilizer. A solution of the modified block copolymer in cyclohexane was subjected to steam stripping to remove cyclohexane therefrom, which produced a modified block copolymer (polymer 9) having the properties shown in Table 1 . In this case, the proportion of the unmodified block copolymer included in Polymer 9 was 30% by weight.

10) Polymer 10

Polymer 10 was prepared following the same procedure as Polymer 1, except that 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as M5) was used as a modifier. The properties of Polymer 10 are given in Table 1.

Table 1 Sample No. Styrene content (wt.%) Proportion of vinyl bonds (%) Weight average molecular weight (×10,000) Types of Modifiers Hydrogenation rate (%) Polymer 1 20 50 8 M1 98 Polymer 2 20 50 8 none 98 Polymer 3 20 50 8 M2 98 Polymer 4 20 50 8 none 98 Polymer 5 40 17 15 M1 0 Polymer 6 40 17 15 _SiCl4 0 Polymer 7 80 35 20 M3 98 Polymer 8 30 40 10 M4 98 Polymer 9 15 30 18 M1 0 Polymer 10 20 50 8 M5 98

11) Polymer 11

After the autoclave equipped with a stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 14.7 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 72 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 13.3 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, the modifier M5 was reacted in an equivalent molar amount of n-butyllithium for the polymerization reaction. The resulting modified block copolymer had a styrene content of 28% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 38%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The resulting solution of the hydrogenated modified block copolymer in cyclohexane was then heated to remove cyclohexane, thus producing a hydrogenated modified block copolymer (polymer 11). Analysis of Polymer 11 showed the results shown in Table 2. In this case, the proportion of the unmodified block copolymer included in Polymer 11 was 20% by weight.

12) Polymer 12

Polymer 12 was prepared following the same procedure as Polymer 11 except without the modifier. The properties of Polymer 12 are given in Table 2.

13) Polymer 13

Polymer 13 was prepared following the same procedure as polymer 11, except that instead of modifier M5, _SiCl4 was used in 1/4 equivalent molar amount relative to n-butyllithium used for polymerization. The properties of Polymer 13 are given in Table 2.

14) Polymer 14

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 20.5 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 61 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 18.5 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. The modifier M1 is then reacted in an equivalent molar amount of n-butyllithium for the polymerization reaction. The resulting modified block copolymer had a styrene content of 39% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 37%.

To the block copolymer obtained above was added hydrogenation catalyst II in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The resulting solution of the hydrogenated modified block copolymer in cyclohexane was then heated to remove the cyclohexane, which produced the hydrogenated modified block copolymer (polymer 14). Analysis of Polymer 14 showed the results shown in Table 2. In this case, the proportion of the unmodified block copolymer included in polymer 14 was 25% by weight.

15) Polymer 15

After the autoclave equipped with a stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 17.8 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 66 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add Polymerization was carried out for 1 hour at °C. In addition, a solution containing 16.2 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. The modifier M4 is then reacted in an equivalent molar amount of n-butyllithium for the polymerization reaction. The resulting modified block copolymer had a styrene content of 34% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 42%.

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The resulting solution of the hydrogenated modified block copolymer in cyclohexane was then heated to remove the cyclohexane, which produced the hydrogenated modified block copolymer (polymer 15). Analysis of Polymer 15 showed the results shown in Table 2. In this case, the proportion of the unmodified block copolymer included in Polymer 15 was 25% by weight.

16) Polymer 16

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 35.1 parts by weight of previously purified styrene (20% by weight concentration) in cyclohexane. After adding n-butyllithium and tetramethylethylenediamine and polymerizing for 1 hour at 70° C., add 33 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and then add it at 70° C. Polymerization was carried out for 1 hour at °C. In addition, a solution containing 31.9 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. Then, the modifier M5 was reacted in an equivalent molar amount of n-butyllithium for the polymerization reaction. The resulting modified block copolymer had a styrene content of 67% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 18%. .

To the modified block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. under a hydrogen pressure of 0.7 MPa for 1 hour. Then, methanol was added, followed by 3-(3,5-di-t-butyl-4-hydroxyphenyl) octadecyl propionate as a stabilizer to 0.3 wt. Servings are added. The resulting solution of the hydrogenated modified block copolymer in cyclohexane was then heated to remove the cyclohexane, which produced the hydrogenated modified block copolymer (polymer 16). Analysis of Polymer 16 showed the results shown in Table 2. In this case, the proportion of the unmodified block copolymer included in polymer 16 was 30% by weight.

17) Polymer 17

Polymer 17 was prepared according to the same procedure as Polymer 16, except that hydrogenation catalyst I was added in an amount of 100 ppm Ti and the hydrogenation reaction was carried out at a temperature of 65° C. and a hydrogen pressure of 0.7 MPa, wherein the hydrogenation rate was 60%. The properties of Polymer 17 are given in Table 2.

18) Polymer 18

After the autoclave equipped with stirrer and jacket had been cleaned, dried and flushed with nitrogen, it was charged with a solution comprising 20 parts by weight of previously purified styrene (concentration 20% by weight) in cyclohexane. After the subsequent addition of n-butyllithium and polymerization at 70°C for 1 hour, the addition of 30 parts by weight of previously refined butadiene (concentration 20% by weight) in cyclohexane and subsequent polymerization at 70°C for 1 hour . In addition, a solution containing 50 parts by weight of styrene in cyclohexane was added and then a polymerization reaction was performed at 70° C. for 1 hour. The resulting block copolymer had a styrene content of 70% by weight, wherein the proportion of vinyl bonds in the polybutadiene fraction was 11%. In addition, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by weight based on 100 parts by weight of the block copolymer. The resulting solution of the block copolymer in cyclohexane was then heated to remove the cyclohexane, which produced the block copolymer (polymer 18). Analysis of Polymer 18 showed the results shown in Table 2.

19) Polymer 19

Polymer 19 was prepared following the same procedure as Polymer 11 except controlling the amount of n-butyllithium to reduce the molecular weight. The properties of Polymer 19 are given in Table 2.

20) Polymer 20

Polymer 20 was prepared following the same procedure as Polymer 19 except without the modifier. The properties of Polymer 20 are given in Table 2.

Table 2 sample number Styrene content (wt%) Proportion of vinyl bonds (%) Weight average molecular weight (×10,000) Types of Modifiers Block ratio of styrene homopolymer (%) Hydrogenation rate (%) 1,2C=Proportion of C units (%) Polymer 11 28 38 18 M5 99 98 0 Polymer 12 28 38 18 none 99 98 0 Polymer 13 28 38 38 _SiCl4 99 98 0 Polymer 14 39 37 40 M1 93 98 0 Polymer 15 34 42 25 M4 91 98 0 Polymer 16 67 18 8 M5 91 98 0 Polymer 17 67 18 8 M5 91 60 0.5 Polymer 18 70 11 11 none 90 0 12 Polymer 19 28 38 8 M5 99 98 0 Polymer 20 28 38 8 none 99 98 0

[Example 1]

A solution of polymer 1 in cyclohexane was mixed with silica A in an amount of 15 parts by weight based on 100 parts by weight of polymer. A part of this mixed solution was sampled and left for a day and a night. Silica A remained uniformly finely dispersed and little silica A separated and precipitated from the mixed solution. Therefore, it can be confirmed that the polymer 1 and the silica A are intimately bound together to form a composite state.

Then, the mixed solution of polymer 1 and silica A was heated to remove cyclohexane, thus obtaining a block copolymer composition. The physical properties of the resulting compositions are given in Table 3.

[Comparative Example 1]

Similar to Example 1, Silica A was added to the solution of Polymer 2 to obtain a mixture. A portion of this solution was sampled and left for a day and a night. As a result, silica A was precipitated and the composite state as in Example 1 did not occur.

Then, the above mixed solution of polymer 2 and silica A was heated to remove cyclohexane, thus obtaining a block copolymer composition. The physical properties of the resulting compositions are given in Table 3.

[Comparative Examples 2 and 3]

The block copolymer composition (comparative example 2) wherein the addition amount of silica A is lower than the number range in the formula determined by the present invention, and the block copolymer composition wherein the addition amount of silica A is higher than the range (Comparative Example 3) was prepared according to the same steps as in Example 1. The resulting composition had the physical properties shown in Table 3.

[Example 2]

A solution of polymer 3 in cyclohexane was mixed with silica A in an amount of 35 parts by weight based on 100 parts by weight of polymer. A portion of this solution was sampled and left for a day and a night. Silica A remained homogeneously finely dispersed and little Silica A separated and precipitated out of solution. Therefore, it can be confirmed that the polymer 3 and the silica A are intimately bound together to form a composite state.

Then, the mixed solution of polymer 3 and silica A as described above was heated to remove cyclohexane, thus obtaining a block copolymer composition. The physical properties of the resulting compositions are given in Table 3.

In addition, examination of the abrasion resistance of the composition revealed that the abrasion amount was 14 mg.

[Comparative example 4]

Similar to example 2, to a solution of polymer 4 in cyclohexane was added silica A to obtain a mixture. A portion of this solution was sampled and left for a day and a night. As a result, silica A was precipitated and the composite state as in Example 2 did not occur.

Then, the above mixed solution of polymer 4 and silica A was heated to remove cyclohexane, thus obtaining a block copolymer composition. The physical properties of the resulting compositions are given in Table 3.

In addition, examination of the abrasion resistance of the composition showed that the abrasion amount was 25 mg.

[Example 3]

100 parts by weight of polymer 5 and 30 parts by weight of silica B were mixed in a twin-screw extruder with two L/D 34 and 30 mm screws rotating in the same direction to obtain a block copolymer composition. The extruder was operated at an extrusion temperature of 210° C., and a rotation speed of 200 rpm. The resulting composition had a haze of 55%.

[Comparative Example 5]

For Polymer 6, the block copolymer composition was obtained following the same procedure as in Example 3. The resulting composition had a haze of 80%, so it was not as clear as the composition of Example 3.

[Example 4]

A solution of polymer 7 in cyclohexane was mixed with silica B in an amount of 75 parts by weight based on 100 parts by weight of polymer. A portion of this solution was sampled and left for a day and a night. Silica B remained uniformly finely dispersed and little silica B separated and precipitated out of solution. Therefore, it can be confirmed that the polymer 7 and the silica A are intimately bound together to form a composite state.

[Example 5]

A solution of polymer 8 in cyclohexane was mixed with silica C in an amount of 100 parts by weight of polymer 810 parts by weight. A portion of this solution was sampled and left for a day and a night. Silica C remained homogeneously finely dispersed and little Silica C separated and precipitated from solution. Therefore, it can be confirmed that the polymer 8 and the silica C are intimately bound together to form a composite state.

[Example 6]

A solution of polymer 9 in cyclohexane was mixed with silica A in an amount of 920 parts by weight based on 100 parts by weight of polymer. A portion of this solution was sampled and left for a day and a night. Silica A remained homogeneously finely dispersed and little Silica A separated and precipitated out of solution. Therefore, it can be confirmed that the polymer 9 and the silica A are intimately bound together to form a composite state.

[Example 7]

A solution of polymer 10 in cyclohexane was mixed with silica A in an amount of 105 parts by weight based on 100 parts by weight of polymer. A portion of this solution was sampled and left for a day and a night. Silica A remained homogeneously finely dispersed and little Silica A separated and precipitated out of solution. Therefore, it can be confirmed that the polymer 10 and the silica A are intimately bound together to form a composite state.

table 3 composition components Physical properties of the composition Components (1) Components (2) Transparency Haze (%) Heat resistance Δ inflection point temperature (°C) Machinability type Content (parts by weight) type Content (parts by weight) Example 1 Polymer 1 100 Silica A 5 45 175 ○ Comparative example 1 Polymer 2 100 Silica A 5 77 130 ○ Comparative example 2 Polymer 1 100 Silica A 0.1 5 100 ○ Comparative example 3 Polymer 1 100 Silica A 60 can't get in good shape x Example 2 Polymer 3 100 Silica A 5 43 160 ○ Comparative example 4 Polymer 4 100 Silica A 5 75 125 ○

[Example 8 and 9]

100 parts by weight of Polymer 11 and rubber softener (PW-380) were melt-kneaded at 230° C. and under the composition shown in Table 4 in a twin-screw extruder with a 30 mm screw. Then add the silica A or C of the amount shown in Table 4 as component (2), the polypropylene resin of the amount shown in Table 4 as component (3), and 0.88 parts by weight of 3-(3,5-di-t- Octadecyl butyl-4-hydroxyphenyl)propionate was used as a stabilizer. The resulting mixture was melt-kneaded at 230° C. in a twin-screw extruder having a 25 mm screw to obtain a block copolymer composition. The physical properties of the resulting compositions are given in Table 4.

[Comparative Example 6]

Block copolymer compositions were prepared following the same procedure as in Examples 8 and 9, except that no silica was incorporated. The physical properties of the resulting compositions are given in Table 4.

[Comparative Example 7]

The block copolymer composition was prepared according to the same steps as in Examples 8 and 9, except that the amount of silica B added was 80 parts by weight. The physical properties of the resulting compositions are given in Table 4.

[Comparative Example 8]

A block copolymer composition was prepared following the same procedure as in Example 8 using Polymer 12. The physical properties of the resulting compositions are given in Table 4.

[Comparative Example 9]

A block copolymer composition was prepared following the same procedure as in Example 8 using Polymer 13. The physical properties of the resulting compositions are given in Table 4.

[Example 10]

100 parts by weight of Polymer 14 and 100 parts by weight of rubber softener (PW-380) were melt-kneaded at 230° C. in a twin-screw extruder with a 30 mm screw. Then add 15 parts by weight of silica A as component (2), 34 parts by weight of polypropylene resin as component (3), and 0.88 parts by weight of 3-(3,5-di-t-butyl-4-hydroxyphenyl ) stearyl propionate as a stabilizer. The resulting mixture was melt-kneaded at 230° C. in a twin-screw extruder having a 25 mm screw to obtain a block copolymer composition. The physical properties of the resulting compositions are given in Table 4.

[Example 11]

100 parts by weight of Polymer 15 and 100 parts by weight of rubber softener (PW-380) were melt-kneaded at 230° C. in a twin-screw extruder having a 30 mm screw to obtain a mixture. Then, 15 parts by weight of silica A as component (2), 34 parts by weight of polypropylene resin as component (3), and 0.88 parts by weight of 3-(3,5-di-t-butyl- Octadecyl 4-hydroxyphenyl)propionate was used as a stabilizer, and then all were melt-kneaded at 230° C. in a twin-screw extruder with a 25 mm screw to obtain a block copolymer composition. The physical properties of the resulting compositions are given in Table 4.

Table 4 Example 8 Example 9 Example 10 Example 11 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Composition (parts by weight) Polymer n 100 100 - - 100 100 - - Polymer 12 - - - - - - 100 - Polymer 13 - - - - - - - 100 Polymer 14 - - 100 - - - - - Polymer 15 - - 100 - - - - Silica A 15 - 15 15 - - 15 15 Silica B - - - - - 80 - - Silica C - 50 - - - - - - Polypropylene 34 30 34 34 34 26 34 34 rubber softener 100 136 100 100 88 165 100 100 Hardness (JIS A) 62 59 63 63 63 59 62 63 Permanent compression set (%) 29 26 28 29 37 27 35 35 Tensile breaking strength (MPa) 13 8 14 14 13 6 15 15 Processing performance ○ ○ ○ ○ ○ x ○ x Average particle size of filler in dispersion (μm) 0.2 0.2 0.1 0.2 0.3 0.4 0.4 0.4

[Examples 12 and 13]

100 parts by weight of Polymer 11 and 100 parts by weight of a rubber softener (PW-380) were melt-kneaded at 230° C. in a twin-screw extruder with a 30 mm screw. Then add the silica of the amount shown in table 5 as component (2), the polypropylene resin of the amount shown in table 5 as component (3), 3 parts by weight of polystyrene resin, 7 parts by weight of polyphenylene ether resin, and 0.88 parts by weight of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as a stabilizer. The resulting mixture was melt-kneaded at 270° C. in a twin-screw extruder having a 25 mm screw to obtain a block copolymer composition. The physical properties of the resulting compositions are given in Table 5.

[Comparative Example 10]

A block copolymer composition was prepared following the same procedure as in Example 12, except that Polymer 12 was used. The physical properties of the resulting compositions are given in Table 5.

[Comparative Example 11]

A block copolymer composition was prepared following the same procedure as in Example 12 using Polymer 18. The physical properties of the resulting compositions are given in Table 5.

table 5 Example 12 Example 13 Comparative example 10 Comparative example 11 Composition (parts by weight) Polymer 11 100 100 - - Polymer 12 - - 100 - Polymer 18 - - - 100 Silica B 15 40 15 15 Polypropylene 34 30 34 34 rubber softener 100 136 100 100 polystyrene 3 3 3 3 polyphenylene ether 7 7 7 7 Hardness (JIS A) 62 60 62 Gellation& Decomposition Permanent compression set (%) 30 26 37 Average particle size of filler in dispersion (μm) 0.3 0.2 0.3

[Example 14]

Add 100 parts by weight of polymer 16, 10 parts by weight of silica A as component (2), 271 parts by weight of polypropylene resin and 834 parts by weight of polystyrene resin as component (3), and 0.88 parts by weight of 3-(3, 5-di-t-butyl-4-hydroxyphenyl) octadecyl propanoate as stabilizer and the resulting mixture was melt kneaded at 230° C. in a twin-screw extruder with a 25 mm screw to give Block copolymer compositions. The physical properties of the resulting compositions are given in Table 6.

[Example 15]

A block copolymer composition was prepared following the same procedure as in Example 14 using Polymer 17. The physical properties of the resulting compositions are given in Table 6.

[Comparative Example 12]

A block copolymer composition was prepared following the same procedure as in Example 15, except that no silica was used. The physical properties of the resulting compositions are given in Table 6.

[Comparative Example 13]

A block copolymer composition was prepared following the same procedure as in Example 15, except that polymer 18 was used, but no silica was used. The physical properties of the resulting compositions are given in Table 6.

Table 6 Example 14 Example 15 Comparative example 12 Comparative example 13 Composition (parts by weight) Polymer 16 100 - - - Polymer 17 - 100 100 - Polymer 18 - - - 100 Silica A 10 10 - - Polypropylene 271 271 271 271 polystyrene 834 834 834 834 Bending strength (MPa) 82 82 73 71 Izod impact strength (J/m) 157 158 149 149

[Example 16]

Add 100 parts by weight of polymer 19, 10 parts by weight of silica C as component (2), and 0.88 parts by weight of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propane An acid ester was used as a stabilizer and the resulting mixture was melt-kneaded at 220° C. in a twin-screw extruder having a 25 mm screw to obtain a block copolymer composition. The physical properties of the resulting compositions are given in Table 7.

[Example 17]

A block copolymer composition was prepared following the same procedure as in Example 16, except that Si69 was added in an amount of 10% by weight based on the silica C. The physical properties of the resulting compositions are given in Table 7.

[Comparative Example 14]

A block copolymer composition was prepared following the same procedure as in Example 16 using Polymer 20. The physical properties of the resulting compositions are given in Table 7.

[Comparative Example 15]

A block copolymer composition was prepared following the same procedure as in Example 17 using Polymer 20. The physical properties of the resulting compositions are given in Table 7.

Table 7 Example 16 Example 17 Comparative example 14 Comparative example 15 composition Polymer 19 (parts by weight) 100 100 - - Polymer 20 (parts by weight) - - 100 100 Silica C (parts by weight) 10 10 10 10 Si69(%wt/silica) - 10 - 10 Tensile strength (MPa) 28 32 17 17 Tensile elongation (%) 590 590 610 610

As can be seen from the results of Examples 1-17 and Comparative Examples 1-15 as described above, the block copolymer composition of the present invention has excellent heat resistance, mechanical strength, transparency, abrasion resistance, and processability, And the block copolymer composition further incorporating an olefin polymer has excellent mechanical strength, permanent compression set, impact resistance, and processability.

Industrial Applicability

The modified block copolymer composition of the present invention has excellent heat resistance, mechanical strength, transparency, abrasion resistance, and processability, and contains a specific amount of (1) a specific structured modified block copolymer containing a specific functional group or its hydrogenated product and (2) at least one filler selected from silica-based inorganic fillers, metal oxides, and metal hydroxides. In addition, by introducing an olefin polymer into the above composition, mechanical strength, permanent compression set, impact resistance, and processability can be further improved.

By utilizing the characteristics as described above, the modified block copolymer composition of the present invention can be processed into various shaped articles by injection molding, extrusion molding and the like. Therefore, it can be used for automobile parts, home appliances, wire jackets, medical parts, footwear, various items, and the like.

Claims (8)

1. A modified block copolymer composition, comprising: (1) A modified block copolymer consisting of a polymer block A mainly comprising vinyl aromatic hydrocarbon and a polymer block B mainly comprising conjugated diene, or a hydrogenated product thereof, and (2) at least one filler selected from silica-based inorganic fillers, metal oxides and metal hydroxides, Wherein the molecular chain of component (1) has functional group at its end, and described functional group has at least one group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilyl group; Component (1) ) has a vinyl aromatic content of 5-95% by weight; the amount of component (2) is 0.5-50 parts by weight based on 100 parts by weight of component (1); and the average particle size of component (2) in the dispersion The size is 0.01-2 μm. 2. The modified block copolymer composition according to claim 1, further comprising (3) an olefin polymer, wherein the amount of component (3) is 10 to 500 parts by weight based on 100 parts by weight of component (1). 3. The modified block copolymer composition according to claim 1 or 2, wherein the block ratio of the vinyl arene in component (1) is not less than 50% of the whole vinyl arene. 4. The modified block copolymer composition according to claim 1 or 2, wherein component (1) is a hydrogenated product of a modified block copolymer having a hydrogenation rate of not less than 10%, and has a vinyl bond structure The proportion of units to the entire structural units derived from conjugated diene in the hydrogenated product is 10-85%, and the proportion of 1,2C=C units is not higher than 15%. 5. The modified block copolymer composition according to claim 1 or 2, wherein the molecular chain of component (1) has a functional group at its end, selected from groups with the following structural formulas (1)-(14): -NR ⁹ R ¹⁰ -OH ----(1) -N[R ¹⁰ -OH] ₂ ----(2)

-NR ⁹ -R ¹⁰ -Si(OR ¹¹ ) ₃ ----(10) -N[R ¹⁰ -Si(OR ¹¹ ) ₃ ] ₂ ----(11)

-OR ¹⁰ -Si(OR ¹¹ ) ₃ ----(14) in R ⁹ , R ¹² -R ¹⁴ are hydrogen, a hydrocarbon group having 1-24 carbon atoms, or having a group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and having 1-24 carbon atoms The hydrocarbon group of the functional group; R ¹⁰ is a hydrocarbon chain with 1-30 carbon atoms, or has a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and a hydrocarbon chain with 1-30 carbon atoms; The hydrocarbon group R ⁹ , R ¹² -R ¹⁴ and the hydrocarbon chain R ¹⁰ have elements such as oxygen, nitrogen or silicon bonded in a bonded form other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group; and R ¹¹ is hydrogen or an alkyl group having 1-8 carbon atoms. 6. The modified block copolymer composition according to claim 1 or 2, wherein the molecular chain of component (1) has a functional group at its end, selected from groups with the following structural formulas (1)-(9): -NR ⁹ -R ¹⁰ -OH ----(1) -N[R ¹⁰ -OH] ₂ ----(2)

in R ⁹ , R ¹² -R ¹⁴ are hydrogen, a hydrocarbon group having 1-24 carbon atoms, or having a functional group selected from hydroxyl, epoxy, silanol, and alkoxysilyl and having 1-24 Hydrocarbon groups of carbon atoms; ^R is a hydrocarbon chain with 1-30 carbon atoms, or has a functional group selected from hydroxide group, epoxy group, silanol group, and alkoxysilyl group and a hydrocarbon with 1-30 carbon atoms chain; The hydrocarbon group R ⁹ , R ¹² -R ¹⁴ and the hydrocarbon chain R ¹⁰ have elements such as oxygen, nitrogen or silicon bonded in a bonded form other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group; and R ¹¹ is hydrogen or an alkyl group having 1-8 carbon atoms. 7. The modified block copolymer composition according to claim 1 or 2, wherein component (2) is at least one selected from silica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide , zinc oxide, slag wool, glass fiber, magnesium hydroxide, aluminum hydroxide, hydrated magnesium silicate, hydrated aluminum silicate, basic magnesium carbonate, and hydrotalcite as fillers. 8. The modified block copolymer composition according to claim 1 or 2, comprising 0.1-20% by weight of the silane coupling agent based on the amount of component (2).